• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Synthesis of the zeolite with the crystal structure cha, synthesis procedure and its use in catalytic applications. The present invention relates to a new synthesis process of a crystalline material of cha structure comprising the following steps: I) preparation of a mixture comprising a water source, a source of a tetravalent element y, a source of an alkaline or alkaline earth cation (a), a source of a trivalent element x, and an organic molecule (adeo1) with the structure [r1 r2 r3 r4 n {sup,] q, Whose molar composition is: N2 o3: yo2: ah: Ii) crystallization of the mixture obtained in i) in a reactor Iii) recovery of the crystalline material obtained in ii). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2574500A1
    申请号:ES201431861
    申请日:2014-12-17
    公开日:2016-06-20
    发明作者:Avelino Corma Canós；Manuel MOLINER MARÍN；Nuria MARTÍN GARCÍA
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    Technical Field
    The present invention relates to a new method of synthesis of the zeolite with chabacite crystalline structure, as well as the use as a catalyst of the zeolitic material
    10 synthesized according to the present synthesis procedure. Background
    Zeolites or molecular sieves are described as materials formed by tetrahedra
    TO4 (T = Si, Al, P, Ge, B, Ti, Sn ...), interconnected by oxygen atoms, creating pores and cavities of uniform size and shape in the molecular range. These zeolitic materials have important applications as catalysts, adsorbents or ion exchangers among others.
    20 Zeolites can be classified according to the size of their channels and pores. In this sense, zeolites with channels limited by 8-T atoms are called "small pore zeolites" (openings around 4 Å), zeolites with channels limited by 10-T atoms are "medium-pore zeolites" (openings around 5.5 Å), those whose channels are limited by 12-T atoms are "large pore zeolites" (openings around
    25 7 Å) and finally, those zeolites whose channels are limited by more than 12-T atoms are called “extra-large pore zeolites” (with openings greater than 7 Å).
    Among the more than 200 zeolitic structures accepted by the International Association ofZeolites (IZA), the chabacita crystal structure is one of the most interesting for its use
    30 in very diverse applications, standing out as a heterogeneous catalyst in the processes methanol to olefins (MTO) and the selective catalytic reduction (RCS) of NOx.
    The IZA has granted the CHA code to the chabacita molecular sieve, which has a crystalline structure formed by a three-way system of small pores
    35 interconnected by large cavities. The CHA structure has been synthesized with various chemical compositions, highlighting as aluminosilicate (“SSZ-13”; Zones, U.S. Patent
    2 


    4544538, 1985, assigned to Chevron) or silicoaluminophosphate ("SAPO-34"; Lok et al. U.S. Patent 4440871, 1984, assigned to UOP).
    In general, it can be said that aluminosilicates have a higher
    5 hydrothermal stability and better acidic properties than homologous silicoaluminophosphates (Katada et al. J. Phys. Chem. C, 2011, 115, 22505). In this way, the synthesis of the CHA structure in its aluminosilicate form in an economical way and with good physical-chemical properties, would be of great interest for its application in industrial processes.
    10 Chabacita is a natural zeolite that has the following chemical composition Ca6Al12Si24O72. In addition to the natural form of the chabacita, this zeolitic structure has been synthesized in the laboratory using different alkaline inorganic cations as inorganic structure director (ADE) agents. Thus, the synthesis of zeolite has been described.
    15 K-G (J. Chem. Soc. 1956, 2822), which is a chabacita synthesized in the presence of potassium cations and has an Si / Al ratio of 1.1-2.1; zeolite D (British Patent 868846, 1961), which is a chabacita synthesized in the presence of sodium-potassium cations and has a Si / Al ratio of 2.2-2.5; and zeolite R (U.S. Patent 3030181, 1962, assigned to Union Carbide) and which has a Si / Al ratio of 1.7-1.8.
    20 Possibly, the first use of organic structure directing agents (ADEO) in the synthesis of zebaite chabacite was described by Tsitsishrili et al. (Soobsch. Akad. Nauk. Cruz. SSR, 1980, 97, 621), showing the presence of tetramethylammonium cations (TMA) in the K2O-Na2O-SiO2-Al2O3-H2O reaction mixture. However, the Si / Al ratio obtained in the
    25 final solid is very low (Si / Al ~ 2.1). The article describes that the presence of TMA in the synthesis medium seems to have an influence on the crystallization of CHA, but said organic molecule is not incorporated into the synthesized material.
    In general, aluminosilicates with low Si / Al ratio (less than 5) have a low
    30 hydrothermal stability. Thus, in order to increase said Si / Al ratio in the synthesis of CHA, more bulky ADEOs were introduced into the synthesis medium, such as N, N, N-tri-alkyl-1-adamantylammonium, N-alkyl -3-quinuclidol and / or N, N, -trialquilexoaminonorbornan (Zones, US Patent 4544538, 1985, assigned to Chevron). Using these ADEOs, the CHA zeolite is obtained with Si / Al ratios between 4-25, which receives the
    35 name of SSZ-13.


    The preferred ADEO for the synthesis of zeolite SSZ-13 is the cation N, N, N-tri-methyl-1-mantamonium (TMAdA). However, said ADEO has a high cost. This high cost may limit the commercial use of the SSZ-13 zeolite in industrial processes. Therefore, the synthesis of zeolite SSZ-13 using cheaper ADEO
    5 would be of great interest for possible commercial applications of said zeolite.
    An alternative to reduce the content of the TMAdA cation in the preparation of the SSZ-13 zeolite is to introduce mixtures of TMAdA with another cheaper ADEO, such as benzyltrimethylammonium (Zones, U.S. Patent 2008/0075656, 2008, assigned to Chevron). In this
    In the invention, it is possible to significantly reduce the content of TMAdA by introducing the benzyltrimethylammonium cation into the synthesis medium. Despite the reduction of the preparation costs of the SSZ-13 zeolite using these mixtures of ADEOs, the presence of the TMAdA cation is still necessary, which has a high cost.
    15 Similarly, the use of mixtures of the TMAdA and tetramethylammonium (TMA) ADEOs in the synthesis medium has been proposed to synthesize the aluminosilicate form of CHA (Bull et al., WO2011 / 064186, 2011, assigned to BASF) . Despite the reduction of the preparation costs of the SSZ-13 zeolite using these mixtures of ADEOs, the presence of the TMAdA cation is still necessary, which has a high cost.
    20 Recently, the synthesis of the aluminosilicate form of CHA has been described using new organic molecules as unique ADEOs in the synthesis medium cheaper than the original ADEO TMAdA. Such organic molecules are benzyltrimethylammonium (Miller et al., U.S. Patent 8007764, 2011, assigned to Chevron), cycloalkylammoniums (Cao et al., U.S.
    25 Patent 2008/0045767, 2008, assigned to ExxonMobil; Feyen et al., WO2013 / 182974, 2013, assigned to BASF), N, N-dimethylpiperidinium (Yilmaz et al. WO2013 / 035054, 2013, assigned to BASF), and N-alkyl-1,4-diazabicyclo cations [2.2 .2] octane and derivatives (Zones, WO2010 / 114996, 2010, assigned to Chevron).
    In addition to the ADEOs described above, the synthesis of the aluminosilicate form of CHA using choline has recently been described (Chen et al. Environ. Sci. Technol., 2014, 48, 13909). In this publication, the authors claim that the use of choline allows for an economic route to synthesize CHA. However, for the efficient synthesis of a material, and its subsequent commercial application in the industry, not only the
    35 sources used in its preparation must be economically attractive, but also the process of preparation of the material must present good yields. In this case, the
    4 


    The initial Si / Al ratio of the material is 20 (as can be calculated from the experimental synthesis procedure of the SSZ-13 described in the publication), and yet the final Si / At the end of the crystalline solid obtained is 6.5. This difference indicates that the synthesis yield is less than 30% (crystalline solid obtained in
    5 function of the inorganic oxides introduced in the gel preparation). This bassperformance using said synthesis procedure for a possible industrial application.In recent years it has been described that zeolitic materials with CHA crystalline structure inthose that have incorporated Cu cations (Cu-CHA), are heterogeneous catalystsEfficient for the selective reduction of NOx in transport-related emissions.
    10 These catalysts have a high hydrothermal stability thanks to the presence of the small pores of the CHA structure, and the stabilization of the Cu cations in the CHA cavities. These catalysts are capable of tolerating temperatures above 700 ° C in the presence of water.
    15 Despite the advances shown in the synthesis of zeolite SSZ-13 through the use of cheaper ADEOs in recent years, there is still a clear need by the chemical industry to improve the synthesis of said crystalline structure, for its application in various catalytic applications, and more particularly for use as a catalyst and / or support in the treatment of NOx in the emission of gases in
    20 cars Description of the Invention
    The present invention relates to a new method of synthesis of a zeolite with
    25 chabacita structure (CHA), which uses a commercial and economic ADEO, as well as the subsequent use of synthesized zeolite as a catalyst in various catalytic processes, such as methanol to olefins, and the selective catalytic reduction (RCS) of NOx in gaseous emissions .
    The present invention relates to a new synthesis process of a crystalline material that has the CHA zeolitic structure and which can comprise at least the following steps:
    i) Preparation of a mixture comprising at least one source of water, at least one source of a tetravalent element Y, at least one source of an alkaline or alkaline earth cation A, at least one source of a trivalent element
    X, and at least one organic molecule (ADEO1) with the structure [R1R2R3R4N +] Q-,
    5 


    where R1, R2, R3 and R4 are selected from linear alkyl groups, and where R1, R2, R3 and R4 each have between 1 and 4 carbon atoms, but at least two of them, must have at least two carbon atoms, and where Q-is an anion, whose molar composition is:
    5 n X2O3: YO2: a A: m ADEO1: z H2O
    where n is in the range of 0 to 0.1, preferably 0.005 to 0.1; and more preferably between 0.01 to 0.1. a is in the range of 0 to 2, preferably 0 to 1; and more
    10 preferably between 0 to 0.8. m is in the range of 0.01 to 2, preferably 0.1 to 1; and more preferably between 0.1 to 0.6. z is in the range of 1 to 200, preferably 1 to 50, and more preferably 2 to 20.
    Ii) Crystallization of the mixture obtained in i) in a reactor iii) Recovery of the crystalline material obtained in ii)
    According to a particular embodiment, the source of the tetravalent element Y may be selected from silicon, tin, titanium, germanium, and combinations thereof. Preferably, the source of element Y is a source of silicon which may be selected from, silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a previously synthesized crystalline material, a material previously synthesized amorphous and combinations thereof, and more preferably it is a material selected from previously synthesized material
    Crystalline, a previously synthesized amorphous material and combinations thereof, and more preferably a previously synthesized crystalline material.
    Some examples of previously synthesized materials could be faujasite-type zeolites (FAU), type L (LTL) and mesoporous amorphous mesoporous materials, such as MCM-41. These 30 previously synthesized materials could also contain other heteroatoms in their structure, such as aluminum.
    According to a particular embodiment, the source of the element Y may be a previously synthesized material, the faujasite, and could contain heteroatoms in its structure, such as aluminum.


    According to a preferred embodiment, the source of the trivalent element X may be selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    According to a particular embodiment, the trivalent element X is aluminum. This source of5 aluminum can be selected from at least any aluminum salt (for examplealuminum nitrate), or any hydrated aluminum oxide.
    According to a particular embodiment of the present invention, ADEO1 may be selected from tetraethylammonium, methyltriethylammonium, propyltriethylammonium, diethyldipropylammonium,
    10 diethyldimethylammonium, and combinations thereof. Preferably said ADEO1 is tetraethylammonium.
    The present invention shows the use of simple organic molecules as ADEOs for the synthesis of the zeolite with chabacite structure, based on tetraalkylammonium cations, where
    The alkyl groups are linear chains comprised between C1 and C4, and where at least two of said alkyl groups is a linear chain C2 or higher.
    In particular, it is shown that the tetraethylammonium cation (TEA) allows the synthesis of the zeolite with chabacite structure with low economic cost, since said molecule
    Organic is commercial, and also requires much cheaper precursors than those required for the preparation of many of the more complex organic molecules described above for the synthesis of a zebaite with chabacita structure. In addition, the present process allows obtaining the discarded crystalline material with high yields (greater than 80%).
    According to the present invention, the crystallization process described in ii) is preferably carried out in autoclaves, under conditions that can be static or dynamic at a temperature selected between 100 and 200 ° C preferably between 130 and 175 ° C and more preferably between 150 and 175 ° C and a crystallization time that can be
    30 between 6 hours and 50 days preferably between 1 and 14 days, and more preferably between 2 and 10 days. It should be borne in mind that the components of the synthesis mixture can come from different sources, which may vary the crystallization conditions described.
    According to a particular embodiment of the process of the present invention, it is possible to add CHA crystals to the synthesis mixture, which act as seeds favoring synthesis
    7 


    described, in an amount up to 25% by weight with respect to the total amount of oxides. These crystals can be added before or during the crystallization process.
    According to the described process, after the crystallization described in ii), the resulting solid is
    5 separates from the mother liquor and recovers. The recovery step iii) can be carried outby different separation techniques known as for example decantation, filtration,ultrafiltration, centrifugation or any other solid-liquid separation technique andcombinations thereof.
    The method of the present invention can also comprise the elimination of the organic content contained inside the material by means of an extraction process. According to a particular embodiment, the removal of the organic compound contained inside the material can be carried out by means of a heat treatment at temperatures above 25 ° C, preferably between 100 and 1000 ° C and for a period of time
    15 preferably between 2 minutes and 25 hours.
    According to another particular embodiment, the material produced according to the present invention can be pelletized using any known technique.
    In the process described above, any cation present in the material can be exchanged by ion exchange for other cations using conventional techniques. Thus, depending on the X2O3 / YO2 molar ratio of the synthesized material, any cation present in the material can be exchanged, at least in part, by ion exchange. These exchange cations are preferably
    25 selected from metals, protons, proton precursors (such as ammonium ions) and mixtures thereof, more preferably said cation is a metal selected from rare earths, metals of groups IIA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    According to a preferred embodiment, the ion exchange cation is copper.
    The present invention also relates to a zeolitic material with CHA structure obtained according to the process described above and which can have the following molar composition
    or X2O3: YO2: p A: q ADEO1: r H2O
    35 where X is a trivalent element;
    8 


    And it is a tetravalent element;A is an alkaline or alkaline earth cation;
    or is in the range of 0 to 0.1, preferably 0.005 to 0.1; and more preferably between 0.01 to 0.1.
    5 p is in the range of 0 to 1, preferably 0 to 0.8; and more preferably between 0 to 0.5. q is between the range of 0.01 to 1, preferably between 0.01 to 0.5; Y
    more preferably between 0.01 to 0.3. r is in the range of 0 to 2, preferably 0 to 1.5; and more
    10 preferably from 0 to 1. According to a preferred embodiment, the material obtained according to the present invention can be calcined. Thus, the zeolitic material with CHA structure can have the following molar composition after being calcined:
    or X2O3: YO2
    15 where X is a trivalent element; And it is a tetravalent element; Y
    or is between the range 0 and 0.1, preferably between 0.005 to 0.1; and more preferably between 0.01 to 0.1.
    According to a particular embodiment, the tetravalent element Y of the zeolitic material with CHA structure may be preferably selected from silicon, tin, titanium, germanium, and combinations thereof, more preferably it is silicon.
    On the other hand, the trivalent element X of the zeolitic material with CHA structure according to the present invention may be preferably selected from aluminum, boron, iron, indium, gallium and combinations thereof, more preferably it is Al.
    The material of the present invention obtained according to the process described above, has the network structure of the zeolite CHA.
    According to a particular embodiment, the crystalline material obtained is substantially free of the presence of phosphorus in the crystalline lattice.
    The present invention also relates to the use of the materials described above and obtained according to the process of the present invention as catalysts for the
    9 


    conversion of feeds formed by organic compounds into products of greater added value, or as a molecular sieve for the elimination / separation of streams (for example gas mixtures) by contacting the feeds with the material obtained.
     According to a preferred embodiment, the material obtained according to the present invention can be used in the production of olefins after contacting it with an oxygenated organic compound under certain reaction conditions. In particular, when feeding methanol, the olefins obtained are mostly ethylene and propylene. Ethylene
     and propylene can be polymerized to form polymers and co-polymers, such as polyethylene and polypropylene.
    According to another preferred embodiment, the material obtained in the present invention can be used as a catalyst in NOx selective catalytic reduction (RCS) reactions.
     (nitrogen oxide) in a gas stream. In particular, the NOx RCS will be performed in the presence of reducing agents, such as ammonium, urea and / or hydrocarbons. Materials to which copper atoms have been introduced according to any of the known techniques are especially useful for this use.
     Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.  Brief description of the figures
    Figure 1: Diffraction pattern of the material obtained in Example 1 of the present invention.
     The present invention is illustrated by the following examples that are not intended to be limiting thereof.


    EXAMPLES Example 1: Synthesis of CHA using tetraethylammonium as ADEO
    1037.2 mg of an aqueous solution of tetraethylammonium hydroxide (TEAOH,
    5 Sigma Aldrich, 35% by weight in water) with 477.1 mg of a 20% aqueous solution inweight of sodium hydroxide (NaOH, Sigma-Aldrich, 98%) and 34 mg of Mili-Q water. The mixture iskept under stirring for homogenization. Finally, 791.0 mg ofzeolite Y (CBV-720, molar ratio SiO2 / Al2O3 = 21) and the mixture is kept under stirringuntil the desired concentration is achieved. The final gel composition is SiO2 / 0.047 Al2O3 /
    10 0.2 TEAOH / 0.2 NaOH / 5 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 160˚C for 7 days. After this time, the product obtained is recovered by filtration and washed with plenty of water. X-ray diffraction shows that the solid obtained presents the characteristic peaks of the CHA structure (see Figure 1). The solid yield obtained is greater than 85%.
    15 The material is calcined at 550 ° C for 4 hours in an air atmosphere to remove the organic matter contained inside.
    Example 2: Synthesis of CHA using tetraethylammonium as ADEO
    20 4494.4mg of an aqueous solution of tetraethylammonium hydroxide (TEAOH, Sigma Aldrich, 35% by weight in water) are mixed with 2047.1 mg of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98% ) and 9525.0 mg of Mili-Q water. The mixture is kept under stirring for homogenization. Finally, 3670.2mg of zeolite Y (CBV-712, molar ratio SiO2 / Al2O3 = 12) are added and the mixture is maintained in
    25 stirring until desired concentration is achieved. The final gel composition is SiO2 / 0.083 Al2O3 / 0.2 TEAOH / 0.2 NaOH / 15 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 160˚C for 7 days. After this time, the product obtained is recovered by filtration and washed with plenty of water. X-ray diffraction shows that the solid obtained has the characteristic peaks of
    30 the CHA structure. The solid yield obtained is greater than 85%.
    The material is calcined at 550˚C for 4h in an air atmosphere to remove organic matter.

    Example 3: Synthesis of triethylpropylammonium hydroxide
    In 250 mL of acetonitrile (CH3CN, Scharlau, 99.9%), 12.8 mL of triethylamine (C6H15N, Sigma Aldricch, 99%) are dissolved. This solution is kept under stirring while 44 mL of 1-iodopropane (C3HI, Sigma Aldrich, 99%) is added dropwise. One time
    After the addition is complete, the mixture is heated at reflux at 80˚C for 3 days. After this time the mixture is partially concentrated in the rotary evaporator and an excess of diethyl ether (C4H10O, Scharlau, 99.5%) is added to precipitate the final product of triethylpropylammonium iodide, which is filtered under vacuum and washed with diethyl ether, obtaining a 88% yield.
    Finally, the ionic exchange of the triethylpropylammonium halide with the corresponding hydroxide is carried out. For this, a solution of 10 g of triethylpropylammonium iodide in 73.7 g of water is prepared and 37 g of exchange resin, Amberlite (Amberlite IRN78 hydroxide form, Supelco) are added to this mixture. The mixture is
    It is kept under stirring overnight, and after this time it is filtered under vacuum to remove the final product, triethylpropylammonium hydroxide, from the resin. The solution obtained is titrated with hydrochloric acid (HCl, Sigma Aldrich, 0.1M) resulting in a concentration of 7.1% by weight and a 75% exchange.
    Example 4: Synthesis of CHA using triethylpropylammonium as ADEO 3064.5 mg of a solution of triethylpropylammonium hydroxide (TEPrOH, 7.1% by weight and prepared according to Example 3 of the present invention) are mixed with 274.0 mg of a 20% solution in water weight of sodium hydroxide (NaOH, 98%). The mixture is kept under stirring for homogenization. Finally, 435.0 mg of
    Y zeolite (CBV-720, SiO2 / Al2O3 molar ratio = 21) and the mixture is kept under stirring until the desired concentration is achieved. The final gel composition is SiO2 / 0.047 Al2O3 /
    0.2 TEPrOH / 0.2 NaOH / 5 H2O. This gel is transferred to a steel autoclave with a Teflon jacket and heated at 160˚C for 7 days. After this time, the product obtained is recovered by filtration and washed with plenty of water. Through
    X-ray diffraction shows that the solid obtained mostly presents the characteristic peaks of the CHA structure.
    The material is calcined at 550˚C for 4h in an air atmosphere to remove organic matter.

    Example 5: Preparation of the zeolite CHA exchanged with Cu (Cu-CHA)
    The sample synthesized and calcined according to the method set forth in Example 1, is washed with 150 g of a 0.04 M aqueous solution of sodium nitrate (NaNO3, Fluka, 99% by weight) per gram of zeolite.
    33.63 mg of copper acetate [(CH3COO) 2Cu · H2O, Probus, 99%) are dissolved in 30 g of water, and 303.3 mg of the previously washed zeolite are added. The suspension is kept under stirring for 24 h. After this time the product obtained is recovered by filtration and washed with plenty of water. Finally the material is calcined in air at
    10 550˚C for 4h.
    Example 6: Catalytic test for the RCS reaction of NOx
    The catalytic activity of the Cu-CHA sample synthesized according to Example 5 of the present invention for the selective catalytic reduction of NOx is studied using a fixed bed quartz tubular reactor 1.2 cm in diameter and 20 cm long. In a typical experiment, the catalyst is compacted into particles of size between 0.25-0.42 mm, introduced into the reactor, and the temperature is increased to 550 ° C (see reaction conditions in Table 1); subsequently, that temperature is maintained for one hour under a flow of nitrogen. Once the temperature has been reached
    20 desired, the reaction mixture is fed. The NOx RCS is studied using NH3 as a reducer. The NOx present at the outlet of the gases from the reactor is analyzed continuously by means of a chemiluminescent detector (Thermo 62C).
    Table 1: Reaction conditions of the NOx RCS.
    Total gas flow (ml / min) 300
    Catalyst Load (mg) 40
    NO concentration (ppm) 500
    NH3 concentration (ppm) 530
    O2 concentration (%) 7
    H2O concentration 5
    Temperature range tested (ºC) 170-550
    The catalytic results of the Cu-CHA catalyst prepared according to Example 5 of the present invention are summarized in Table 2.

    Table 2: Conversion (%) of NOx at different temperatures (200, 250, 300, 350, 400, 450, 500 ° C) using the Cu-CHA catalyst prepared according to Example 3 of the present invention
    Conversion (%) of NOx at different temperatures
    210 ° C 250ºC300ºC350ºC400ºC450 ° C500ºC550 ° C
    Example 3 94.9100.0100.0100.0100.099.795.590.8

    权利要求:
    Claims (24)
    [1]
    1. Synthesis process of a crystalline material that has the CHA zeolitic structure characterized in that it comprises at least the following steps:
     i) Preparation of a mixture comprising at least one source of water, at least one source of a tetravalent element Y, at least one source of an alkaline or alkaline earth cation A, at least one source of a trivalent element X, and at least an organic molecule (ADEO1) with the structure [R1R2R3R4N +] Q-, where R1, R2, R3 and R4 are selected from linear alkyl groups, and where R1,
     R2, R3 and R4 each have between 1 and 4 carbon atoms, but at least two of them must have at least two carbon atoms, and where Q-is an anion, whose molar composition is: n X2O3 : YO2: a A: m ADEO1: z H2O where
     n is in the range of 0 to 0.1. a is in the range of 0 to 2. m is in the range of 0.01 to 2. z is in the range of 1 to 200.
    ii) Crystallization of the mixture obtained in i) in a reactor iii) Recovery of the crystalline material obtained in ii)
    [2]
    2. Process according to claim 1, characterized in that the source of the tetravalent element Y is selected from silicon, tin, titanium, germanium, and combinations thereof.

    [3]
    3. Process according to claim 2, characterized in that the source of the tetravalent element Y is a source of silicon selected from silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a previously synthesized crystalline material , a previously synthesized amorphous material and
     combinations thereof.
    [4]
    4. Process according to claim 3, characterized in that the source of silicon is selected from a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof.

    [5]
    5. Process according to claim 4, characterized in that the previously synthesized materials contain other heteroatoms in their structure.
    [6]
    6. Process according to claim 1, characterized in that the source of the trivalent element5 X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [7]
    7. Process according to claim 6, characterized in that the source of the trivalent element X is aluminum.
    Process according to claim 1, characterized in that the ADEO1 is selected from tetraethylammonium, methyltriethylammonium, propyltriethylammonium, diethyldipropylammonium, diethyldimethylammonium, and combinations thereof.
    [9]
    9. Process according to claim 8, characterized in that said ADEO1 is tetraethylammonium.
    [10]
    10. Process according to claims 1 to 9, characterized in that the crystallization process described in ii) is carried out in autoclaves, under static or dynamic conditions.
    A process according to claims 1 to 10, characterized in that the crystallization process described in ii) is carried out at a temperature between 100 and 200 ° C.
    [12]
    12. Process according to claims 1 to 11, characterized in that the crystallization time of the process described in ii) is between 6 hours and 50 days.
    [13]
    13. Process according to claims 1 to 12, characterized in that it further comprises adding CHA crystals as seeds to the synthesis mixture in an amount up to 25% by weight with respect to the total amount of oxides.
    14. Process according to claim 13, characterized in that the CHA crystals are added before the crystallization process or during the crystallization process.
    [15]
    15. Process according to claim 1, characterized in that the recovery step iii) is
    carried out with a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.

    [16]
    16. Process according to claims 1 to 15, characterized in that it further comprises eliminating the organic content contained inside the material by means of an extraction process.
    17. Process according to claims 1 to 15, characterized in that it further comprises theelimination of the organic content contained inside the material by means of aheat treatment at temperatures between 100 and 1000 ° C for a period of timebetween 2 minutes and 25 hours.
    18. Process according to claims 1 to 17, characterized in that the material obtained is pelletized.
    [19]
    19. Process according to claims 1 to 18, characterized in that any cation
    present in the material can be exchanged by ion exchange for another 15 cations using conventional techniques.
    [20]
    20. Process according to claim 19, characterized in that the exchange cation is selected from metals, protons, proton precursors and mixtures thereof.
    21. Process according to claim 20, characterized in that the exchange cation is a metal selected from rare earths, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    [22]
    22. Process according to claim 21, characterized in that the metal is copper.
    [23]
    23. Zeolitic material with CHA structure obtained according to the process described in claims 1 to 22, characterized in that it has the following molar composition
    or X2O3: YO2: p A: q ADEO1: r H2Owhere
    30 X is a trivalent element; And it is a tetravalent element; A is an alkaline or alkaline earth cation;
    or is in the range of 0 to 0.1;p is in the range of 0 to 1;
    35 q is in the range of 0.01 to 1; and r is in the range of 0 to 2.
    17 

    [24]
    24. Zeolitic material with CHA structure according to claim 23, characterized in that it has the following molar composition after being calcined: n X2O3: YO2 wherein
     X is a trivalent element; And it is a tetravalent element; and n is between the range 0 and 0.1.
    [25]
    25. Zeolitic material with CHA structure according to claims 23 and 24, characterized
     because the tetravalent element Y is selected from silicon, tin, titanium, germanium, and combinations thereof.
    [26]
    26. Zeolitic material with CHA structure according to claims 23 and 24, characterized
    because the trivalent element X is selected from aluminum, boron, iron, indium, gallium and combinations thereof.
    [27]
    27. Zeolitic material with CHA structure obtained according to claims 23 to 26, characterized in that it has the network structure of the CHA zeolite.
    [ 28]
     28. Use of a zeolitic material with CHA structure described in claims 24 to 27 and obtained according to the process described in claims 1 to 22 in processes for the conversion of feeds formed by organic compounds into products of higher added value, or for their elimination / separation of the reactive current by contacting said feed with the described material.

    [29]
    29. Use of a zeolitic material with CHA structure according to claim 28, for the production of olefins after contacting it with an oxygenated organic compound under certain reaction conditions.
    [ 30]
     30. Use of a zeolitic material with CHA structure according to claim 28 for the selective catalytic reduction (RCS) of NOx (nitrogen oxide) in a gas stream.

    FIG. 1
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    CN107108242B|2020-05-22|
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    法律状态:
    2017-09-07| FA2A| Application withdrawn|Effective date: 20170901 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201431861A|ES2574500B1|2014-12-17|2014-12-17|Synthesis of zeolite with the CHA crystalline structure, synthesis procedure and its use in catalytic applications|ES201431861A| ES2574500B1|2014-12-17|2014-12-17|Synthesis of zeolite with the CHA crystalline structure, synthesis procedure and its use in catalytic applications|
    EP18190791.6A| EP3492430A1|2014-12-17|2015-12-11|Zeolite with the cha crystal structure and use thereof in the selective catalytic reduction of nox|
    EP18190792.4A| EP3461791A1|2014-12-17|2015-12-11|Mixture used for synthesis of zeolite with the cha crystal structure|
    EP18190796.5A| EP3483121A1|2014-12-17|2015-12-11|Zeolite with the cha crystal structure and use thereof in the selective catalytic reduction of nox|
    BR112017012800-4A| BR112017012800A2|2014-12-17|2015-12-11|zeolite synthesis with cha crystal structure, synthesis process and its use for catalytic applications|
    EP15808394.9A| EP3233734A1|2014-12-17|2015-12-11|Synthesis of zeolite with the cha crystal structure, synthesis process and use thereof for catalytic applications|
    CA3007852A| CA3007852A1|2014-12-17|2015-12-11|Synthesis of zeolite with the cha crystal structure, synthesis process and use thereof for catalytic applications|
    PCT/EP2015/079425| WO2016096653A1|2014-12-17|2015-12-11|Synthesis of zeolite with the cha crystal structure, synthesis process and use thereof for catalytic applications|
    CN201580069314.XA| CN107108242B|2014-12-17|2015-12-11|Synthesis of zeolites having the CHA crystal structure, methods of synthesis thereof and use thereof in catalytic applications|
    KR1020177017611A| KR20170095903A|2014-12-17|2015-12-11|Synthesis of zeolite with the cha crystal structure, synthesis process and use thereof for catalytic applications|
    US15/533,913| US10322939B2|2014-12-17|2015-12-11|Synthesis of zeolite with the CHA crystal structure, synthesis process and use thereof for catalytic applications|
    EP18190797.3A| EP3461792A1|2014-12-17|2015-12-11|Zeolite with the cha crystal structure and use thereof in the selective catalytic reduction of nox|
    RU2017125256A| RU2017125256A3|2014-12-17|2015-12-11|
    HK18102867.6A| HK1243395A1|2014-12-17|2018-02-28|Synthesis of zeolite with the cha crystal structure, synthesis process and use thereof for catalytic applications|
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    US16/396,899| US10486976B2|2014-12-17|2019-04-29|Synthesis of zeolite with the CHA crystal structure, synthesis process and use thereof for catalytic applications|
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